KR20140093542A - Resist underlayer composition, Process of Producing Integrated Circuit Devices Using the Same, And Integrated Circuit Devices thereof - Google Patents
Resist underlayer composition, Process of Producing Integrated Circuit Devices Using the Same, And Integrated Circuit Devices thereof Download PDFInfo
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0754—Non-macromolecular compounds containing silicon-to-silicon bonds
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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Abstract
Description
A method for manufacturing a semiconductor integrated circuit device using the same, and a semiconductor integrated circuit device manufactured thereby.
Due to the aspect ratio of the pattern, the thickness of the photoresist must be reduced as the line width used in semiconductor microcircuits is reduced. However, if it becomes too thin, it becomes difficult to serve as a mask in a pattern transfer process (etching process). That is, during the etching, the photoresist is exhausted and the substrate can not be etched to a desired depth.
A hard mask process has been introduced to solve this problem. A hard mask is a material that utilizes excellent etch selectivity, mainly using two layers. A carbon-based hard mask is formed on a substrate to be patterned, a silicon-based hard mask is formed thereon, and finally a photoresist is coated. Since the silicon hard mask has a higher etch selectivity to the photoresist than the substrate, the pattern can be easily transferred even by using a thin photoresist. The carbon-based hard mask is etched using the silicon-based hard mask transferred with the pattern as a mask to transfer the pattern, and finally, the pattern is transferred to the substrate using the carbon-based hard mask as a mask. As a result, a thinner photoresist can be used to etch the substrate to a desired depth.
The silicon hard mask functions as an antireflection film by imparting a refractive index (n) and an extinction coefficient (k) value that can control light enhancement and destructive interference. In the three-layer laminate structure of the semiconductor laminated structure (photoresist / silicon hard mask / carbon hard mask), adjustment of n and k of the silicon hard mask is important.
The value of the extinction coefficient (k) of the silicone hard mask is generally controlled depending on the type and content of the phenyl group, which is an organic compound bonded to the silicon atom. However, the incorporation of phenyl groups increases the carbon content and thus has a chemical structure similar to that of the carbon-based hard mask, so that the etch selectivity of the silicon-based hard mask can be lowered.
Therefore, research for increasing the etching resistance of a silicon hard mask has been continued.
One embodiment provides a composition for a resist underlayer film which introduces a cyclic silane having a silicon-silicon bond to increase the silicon content while at the same time realizing the light absorbing characteristic of the silicon hard mask.
Another embodiment provides a method of manufacturing a semiconductor integrated circuit device using the composition for a resist underlayer film.
Another embodiment provides a semiconductor integrated circuit device manufactured by the above manufacturing method.
According to one embodiment, at least one organosilane-based compound selected from the group consisting of compounds represented by the following general formula (1); And a solvent for a resist underlayer film.
[Chemical Formula 1]
(In the formula 1,
R 1 And R 2 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, cyano, thiol, carboxyl, alkoxy, ester, halogenoalkylsulfate, alkylamine, alkylsilylamine, Or an unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 heteroaryl group)
The organosilane compound may further comprise a compound represented by the following general formula (2), (3) or (4).
(2)
[R 3 ] 4 Si
(In the formula (2)
R 3 is hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group,
(3)
[R 4 ] 3 Si-R 5
(3)
R 4 is hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group,
R 5 is a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 heteroaryl group)
[Chemical Formula 4]
[R 6 ] 3 Si-X-Si [R 7 ] 3
(In the formula 4,
R 6 And R 7 are each independently selected from the group consisting of hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group, ,
X is a linear or branched, substituted or unsubstituted C1 to C20 alkylene group; A linear or branched, substituted or unsubstituted C6 to C20 arylene group; Or a C1 to C4 alkyl group containing a substituent selected from the group consisting of an alkenylene group, an alkynylene group, an arylene group, a heterocyclic group, a urea group, an isocyanurate group, C20 alkylene group)
The compound represented by Formula 2 may be used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the total organosilane compound.
The compound represented by Formula 3 may be used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the total organosilane compound.
The compound represented by Formula 4 may be used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the total organosilane compound.
The organosilane compound may have a weight average molecular weight ranging from 2,000 to 50,000.
The organosilane compound may be contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the composition for the entire resist underlayer film.
The composition may further comprise additives selected from the group consisting of cross-linking agents, radical stabilizers, surfactants, and combinations thereof.
The composition for the under-layer resist is prepared by mixing pyridinium p-toluenesulfonate, amidosulfobetain-16, ammonium camphor-10-sulfonate, 10-sulfonic acid ammonium salt, ammonium formate, alkyltriethylammonium formate, pyridinium formate, tetrabutyl ammonium acetate, tetrabutylammonium azide tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, Tetrabutyl ammonium cyanide, tetrabutyl ammonium fluoride, tetrabutyl ammonium iodide ), Tetrabutyl ammonium sulfate, tetrabutyl ammonium nitrate, tetrabutyl ammonium nitrite, tetrabutyl ammonium p-toluene sulfonate, , Tetrabutyl ammonium phosphate, and combinations thereof. ≪ Desc / Clms Page number 7 >
According to another embodiment, there is provided a method comprising: (a) providing a layer of material on a substrate; (b) forming a first resist underlayer film over the material layer; (c) forming a second resist underlayer film on the first resist underlayer film by coating the above-mentioned composition for a resist underlayer film; (d) forming a radiation-sensitive imaging layer over the second resist underlayer film; (e) generating a pattern of radiation-exposed regions in the radiation-sensitive image layer by exposing the radiation-sensitive imaging layer to radiation in a patterned fashion; (f) selectively removing portions of the radiation-sensitive imaging layer and the second resist underlayer film to expose portions of the first resist underlayer film; (g) selectively removing portions of the patterned second resist underlayer film and the first resist underlayer film to expose portions of the material layer; And (h) etching the exposed portion of the material layer to form a patterned material feature.
The method may further include the step of forming an antireflection film between the step (c) of forming the second resist underlayer film and the step (d) of forming the radiation-sensitive imaging layer.
According to another embodiment, there is provided a semiconductor integrated circuit device formed by the above manufacturing method.
It is possible to realize the desired light absorption characteristics at a wavelength of 193 nm while having excellent etching resistance.
Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (F, Cl, Br, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a cyano group, A C3 to C30 cycloalkyl group, a C3 to C30 cycloalkyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C4 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, Substituted with a substituent selected from the group consisting of a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.
In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.
Hereinafter, a composition for a resist underlayer film according to one embodiment will be described.
The composition for a resist underlayer film according to an embodiment includes at least one organosilane compound selected from the group consisting of compounds represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 And R 2 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, cyano, thiol, carboxyl, alkoxy, ester, halogenoalkylsulfate, alkylamine, alkylsilylamine, Or an unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 heteroaryl group.
The organosilane compound is a cyclic structure having a silicon-silicon bond.
The organosilane-based compound has a silicon-silicon bond as described above, so that a predetermined silicon content can be secured. Thus, the etching resistance of the resist lower layer film can be improved. In addition, the organosilane compound has a cyclic structure as described above, so that absorption characteristics and antireflection characteristics required at a wavelength of 193 nm can be realized without introducing a phenyl group or the like.
Since the compound represented by the above formula (1) exhibits an antireflection function due to the absorbance property of silicon-silicon bond, it is possible to omit the application of a separate antireflection coating. An antireflection film may be additionally used for the purpose of improving the absorbance and improving the photo profile.
The solvent is selected from the group consisting of acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, But are not limited to, ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate,? -Butyrolactone, dimethyl ether, dibutyl ether, methanol, ethanol and combinations thereof.
The organosilane compound may further comprise a compound represented by the following general formula (2), (3) or (4).
(2)
[R 3 ] 4 Si
In Formula 2,
R 3 is hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxy group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group or an alkylsilyloxy group.
(3)
[R 4 ] 3 Si-R 5
In Formula 3,
R 4 is hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group,
R 5 is a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 heteroaryl group.
[Chemical Formula 4]
[R 6 ] 3 Si-X-Si [R 7 ] 3
In Formula 4,
R 6 And R 7 are each independently selected from the group consisting of hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group, ,
X is a linear or branched, substituted or unsubstituted C1 to C20 alkylene group; A linear or branched, substituted or unsubstituted C6 to C20 arylene group; Or a C1 to C4 alkyl group containing a substituent selected from the group consisting of an alkenylene group, an alkynylene group, an arylene group, a heterocyclic group, a urea group, an isocyanurate group, C20 alkylene group.
The use of the compound represented by the above formula (2) can increase storage stability. The use of the compound represented by the general formula (3) can increase the storage stability and ensure the light absorbing property. When the compound represented by Formula 4 is used, sufficient etching resistance against oxygen plasma can be secured .
The compound represented by Formula 2, the compound represented by Formula 3, or the compound represented by Formula 4 may be used in an amount of 1 to 99 parts by weight, respectively, based on 100 parts by weight of the total organosilane compound.
The organosilane compound may have a weight average molecular weight ranging from 2,000 to 50,000. Particularly, it is preferable to use the one having a range of 3,000 to 20,000 in order to consider the coating performance on the substrate and to prevent gel formation.
The organosilane compound may be contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the composition for the entire resist underlayer film. Particularly, it is preferable that 1 to 30% by weight is included in consideration of the coating performance on the substrate.
The composition for a resist underlayer film may further comprise an additive selected from the group consisting of a crosslinking agent, a radical stabilizer, a surfactant, and a combination thereof.
Specifically, the crosslinking agent may be selected from the group consisting of tetrabutyl ammonium acetate, tetrabutyl ammonium azide, tetrabutyl ammonium benzoate, tetrabutyl ammonium bisulfate, Tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium cyanide, tetrabutyl ammonium fluoride, tetrabutyl ammonium iodide, tetrabutyl ammonium iodide, Such as tetrabutyl ammonium sulfate, tetrabutyl ammonium nitrite, tetrabutyl ammonium p-toluene sulfonate, tetrabutyl ammonium phosphate) In the group consisting of mixtures, That can be used.
The composition for a resist underlayer film may also contain a sulfonic acid salt of an organic base (for example, pyridinium p-toluenesulfonate, amidosulfobetain-16, 10-sulfonic acid ammonium salt), ammonium formate, alkylammonium formate (for example, triethylammonium formate (for example, triethylammonium formate, trimethylammonium formate, tetramethylammonium formate, tetrabutylammonium formate, etc.), pyridinium formate, alkylammonium nitrate (e.g., For example, tetramethylammonium nitrate, tetrabutyl ammonium nitrate, and the like), and combinations thereof. A crosslinking catalyst as an additive.
The crosslinking catalyst may be added alone or in combination with an additive selected from the group consisting of the crosslinking agent, the radical stabilizer, the surfactant, and a combination thereof, to the composition comprising the organosilane compound and the solvent.
In the case where the composition for a resist underlayer film further comprises the above-mentioned additives, it is preferable from the viewpoint of storage stability that each additive is contained in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the organosilane compound.
Hereinafter, a method for manufacturing a semiconductor integrated circuit device using the resist underlayer film composition described above will be described.
A method of fabricating a semiconductor integrated circuit device according to one embodiment includes the steps of: (a) providing a layer of material on a substrate; (b) forming a first resist underlayer film over the material layer; (c) forming a second resist underlayer film on the first resist underlayer film by coating the above-mentioned composition for a resist underlayer film; (d) forming a radiation-sensitive imaging layer over the second resist underlayer film; (e) generating a pattern of radiation-exposed regions in the radiation-sensitive image layer by exposing the radiation-sensitive imaging layer to radiation in a patterned fashion; (f) selectively removing portions of the radiation-sensitive imaging layer and the second resist underlayer film to expose portions of the first resist underlayer film; (g) selectively removing portions of the patterned second resist underlayer film and the first resist underlayer film to expose portions of the material layer; And (h) etching the exposed portion of the material layer to form a patterned material feature.
First, a material to be patterned, such as aluminum and SiN (silicon nitride), is formed on a silicon substrate according to a conventional method. The material to be patterned in which the composition for a resist underlayer film of the present invention is used may be any conductive, semi-conductive, magnetic or insulating material.
A first resist lower layer film made of an organic material is formed on the material to be patterned. At this time, the first resist underlayer film may be formed to a thickness of 200 ANGSTROM to 12000 ANGSTROM using an organic material mainly containing carbon, hydrogen and oxygen. In this case, the type and the thickness of the first resist underlayer film are not limited to the above-described range, but may be manufactured in various forms, and those skilled in the art will recognize that the technical idea of the present invention, It will be appreciated that the invention may be embodied in other specific forms without modification.
Then, the composition for a lower resist film according to an embodiment of the present invention is spin-on coated to a thickness of 100 A to 4000 A and then heat-treated to form a second resist lower layer film.
The heat treatment for forming the second resist lower layer film may be performed at 100 ° C to 400 ° C. When the heat treatment is performed in the above range, the content of Si in the lower layer film is increased, and a dense lower layer film can be provided.
When the second resist lower layer film is formed, a radiation-sensitive imaging layer is formed and a developing process is performed to expose a region to be patterned by an exposure process through the imaging layer. Then, the imaging layer and the antireflection layer are selectively removed to expose portions of the material layer, and dry etching is performed using an etching gas. Typical examples of the etching gas include CHF 3 , CH 2 F 2 , CF 4 , CH 4 , N 2 , O 2 , Cl 2 , BCl 3, and a mixed gas thereof. After the patterned material feature is formed, any radiation-sensitive imaging layer remaining by a conventional photoresist stripper can be removed.
Another manufacturing method according to an embodiment of the present invention may further include forming an antireflection film on the second resist underlayer film formed after the step (c) of forming the second resist underlayer film. Since the composition for a resist underlayer film according to the present invention contains at least one organosilane compound selected from the group consisting of the compounds represented by the above formula (1), a sufficient antireflection effect can be obtained and no additional antireflection film is required. An additional antireflection film may be further formed for the purpose of improvement and improvement of the photo profile. At this time, the antireflection film can be produced by a conventional method.
An element patterned by such a manufacturing method as described above is provided. The device may be a semiconductor integrated circuit device. In particular, a patterned material layer structure, such as a hole for a metal wiring line, contact or bias; Insulation sections such as multimask trenches or cellrow trench insulation; A trench for a capacitor structure such as a design of an integrated circuit device, and the like. It can also be very usefully applied to form patterned layers of oxides, nitrides, polysilicon and chromium. It should also be understood that the invention is not limited to any particular lithographic technique or device structure.
Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Example One
0.68 g of methyltrimethoxysilane (MT) and 3.95 g of hexamethylhexaethoxycyclohexasilane were added to a 100-ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, After dissolving in 41.65 g of propylene glycol methyl ether acetate (PGMEA), 0.25 g of 100 ppm nitric acid aqueous solution was added to the solution. Thereafter, the reaction was carried out at room temperature for 3 days, to obtain an organosilane-based condensation polymer A 1 (weight average molecular weight = 16000, polydispersity (PD) = 2.3). The organosilane-based polymer was spin-coated on a silicon wafer and baked at a temperature of 240 ° C for 1 minute to form a resist underlayer film having a thickness of 1700 Å.
Example 2
0.87 g of methyltrimethoxysilane (MT) and 3.4 g of hexamethylhexaethoxycyclohexasilane were added to a 100-ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, glycol methyl ether acetate), and 0.26 g of 100 ppm nitric acid solution was added to the solution. Thereafter, the mixture was allowed to react at room temperature for 5 days, to obtain an organosilane-based condensation polymer A 2 (weight average molecular weight = 14000, polydispersity (PD) = 2.3). The organosilane-based polymer was coated on a silicon wafer by spin coating and baked at 240 ° C for 1 minute to form a 1400 Å thick resist underlayer film.
Example 3
1.22 g of methyltrimethoxysilane (MT) and 2.9 g of hexamethylhexaethoxycyclohexasilane were charged in a 100 ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, glycol methyl ether acetate), and 0.29 g of a 100 ppm nitric acid aqueous solution was added to the solution. Thereafter, the reaction was carried out at room temperature for 2 days, to obtain an organosilane-based condensation polymer A 3 (weight average molecular weight = 19000, polydispersity (PD) = 2.7). The organosilane-based polymer was coated on a silicon wafer by spin coating and baked at a temperature of 240 ° C for 1 minute to form a 1600 Å thick resist underlayer film.
Example 4
1.69 g of methyltrimethoxysilane (MT) and 2.19 g of hexamethylhexaethoxycyclohexasilane were charged in a 100 ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, glycol methyl ether acetate) and 0.33 g of 100 ppm nitric acid aqueous solution was added to the solution. Thereafter, the reaction was carried out at room temperature for 6 hours, to obtain an organosilane-based condensation polymer A 4 (weight average molecular weight = 13000, polydispersity (PD) = 3.1). The organosilane-based polymer was coated on a silicon wafer by spin coating and baked at a temperature of 240 캜 for 1 minute to form a 1500 Å thick resist lower layer film.
Comparative Example One
5.90 g of methyltrimethoxysilane (MT) and 1.30 g of phenyltrimethoxysilane (PT) were added to a 100 ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, methyl ether acetate), and 2.34 g of a 100 ppm nitric acid aqueous solution was added to the solution. Thereafter, the reaction was carried out at 80 to 110 ° C for 5 days. After the reaction, an organosilane-based condensation polymer B 1 (weight average molecular weight = 6000, polydispersity (PD) = 1.3) was obtained. The organosilane-based polymer was coated on a silicon wafer by spin coating and baked at a temperature of 240 ° C for 1 minute to form a resist underlayer film having a thickness of 1300 Å.
Comparative Example 2
6.05 g of methyltrimethoxysilane (MT) and 1.09 g of phenyltrimethoxysilane (PT) were added to a 100-ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, methyl ether acetate) and 2.40 g of a 100 ppm nitric acid aqueous solution was added to the solution. Thereafter, the reaction was carried out at 80 to 110 DEG C for 6 days. After the reaction, an organosilane-based condensation polymer B 2 (weight average molecular weight = 9300, polydispersity (PD) = 1.4) was obtained. The organosilane-based polymer was coated on a silicon wafer by spin coating and baked at a temperature of 240 캜 for 1 minute to form a 1500 Å thick resist lower layer film.
Comparative Example 3
6.23 g of methyltrimethoxysilane (MT) and 0.83 g of phenyltrimethoxysilane (PT) were added to a 100-ml three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, methyl ether acetate), and 2.47 g of a 100 ppm nitric acid aqueous solution was added to the solution. Then, the reaction was carried out at 80 to 110 ° C for 8 days. After the reaction, an organosilane-based condensation polymer B 3 (weight average molecular weight = 6400, polydispersity (PD) = 1.9) was obtained. The organosilane-based polymer was coated on a silicon wafer by a spin-coating method and baked at a temperature of 240 ° C for 1 minute to form a resist underlayer film having a thickness of 1550 Å.
Comparative Example 4
6.42 g of methyltrimethoxysilane (MT) and 0.54 g of phenyltrimethoxysilane (PT) were added to a 100-mL three-necked flask equipped with a stirring rod magnet, a cooling tube and a rubber stopper, methyl ether acetate), and 2.55 g of a 100 ppm nitric acid aqueous solution was added to the solution. Then, the reaction was carried out at 90 to 110 ° C for 12 days. After the reaction, an organosilane-based condensation polymer B 4 (weight average molecular weight = 8100, polydispersity (PD) = 1.4) was obtained. The organosilane-based polymer was coated on a silicon wafer by spin coating and baked at a temperature of 240 캜 for 1 minute to form a 1500 Å thick resist underlayer film.
Experimental Example 1: Evaluation of optical characteristics
The refractive index (n) and the extinction coefficient (k) of the resist underlayer films prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured. The instrument used was an Ellipsometer (manufactured by J. A. Woollam), and the measurement results are shown in Tables 1 and 2 below.
(mole%)
(mole%)
Average
Molecular Weight
(193 nm)
(193 nm)
* MT (methyltrimethoxysilane): methyltrimethoxysilane
* Me 6 Si 6 (OEt) 6 : Hexamethylhexaethoxycyclohexasilane
(mole%)
(mole%)
Average
Molecular Weight
(193 nm)
(193 nm)
* MT (methyltrimethoxysilane): methyltrimethoxysilane
※ PT (phenyltrimethoxysilane): phenyltrimethoxysilane
Referring to Tables 1 and 2, it can be seen that the composition for a resist underlayer film according to Examples 1 to 4 has a refractive index and an extinction coefficient characteristic that can be used at a wavelength of 193 nm even though a phenyl group is not introduced.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.
Claims (12)
Solvent-containing
Composition for a resist underlayer film.
[Chemical Formula 1]
(In the formula 1,
R 1 And R 2 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, cyano, thiol, carboxyl, alkoxy, ester, halogenoalkylsulfate, alkylamine, alkylsilylamine, Or an unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 heteroaryl group)
Wherein the organosilane compound further comprises a compound represented by the following formula (2), (3) or (4).
(2)
[R 3 ] 4 Si
(In the formula (2)
R 3 is hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group,
(3)
[R 4 ] 3 Si-R 5
(3)
R 4 is hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group,
R 5 is a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 heteroaryl group)
[Chemical Formula 4]
[R 6 ] 3 Si-X-Si [R 7 ] 3
(In the formula 4,
R 6 And R 7 are each independently selected from the group consisting of hydrogen, a halogen group, a hydroxy group, a cyano group, a thiol group, a carboxyl group, an alkoxy group, an ester group, a halogenoalkylsulfite group, an alkylamine group, an alkylsilylamine group, ,
X is a linear or branched, substituted or unsubstituted C1 to C20 alkylene group; A linear or branched, substituted or unsubstituted C6 to C20 arylene group; Or a C1 to C4 alkyl group containing a substituent selected from the group consisting of an alkenylene group, an alkynylene group, an arylene group, a heterocyclic group, a urea group, an isocyanurate group, C20 alkylene group)
Wherein the compound represented by Formula 2 is used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the total organosilane compound.
Wherein the compound represented by Formula 3 is used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the total organosilane compound.
Wherein the compound represented by Formula 4 is used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the total organosilane compound.
Wherein the organosilane compound has a weight average molecular weight ranging from 2,000 to 50,000.
Wherein the organosilane compound is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the composition for the entire resist underlayer film.
Wherein the composition for a resist underlayer film further comprises an additive selected from the group consisting of a crosslinking agent, a radical stabilizer, a surfactant, and combinations thereof.
The composition for the under-layer resist is prepared by mixing pyridinium p-toluenesulfonate, amidosulfobetain-16, ammonium camphor-10-sulfonate, 10-sulfonic acid ammonium salt, ammonium formate, alkyltriethylammonium formate, pyridinium formate, tetrabutyl ammonium acetate, tetrabutylammonium azide tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium bromide, Tetrabutyl ammonium cyanide, tetrabutyl ammonium fluoride, tetrabutyl ammonium iodide ), Tetrabutyl ammonium sulfate, tetrabutyl ammonium nitrate, tetrabutyl ammonium nitrite, tetrabutyl ammonium p-toluene sulfonate, , Tetrabutyl ammonium phosphate, and combinations thereof. ≪ Desc / Clms Page number 13 >
(b) forming a first resist underlayer film over the material layer;
(c) coating a resist underlayer film composition according to any one of claims 1 to 9 on the first resist underlayer film to form a second resist underlayer film;
(d) forming a radiation-sensitive imaging layer over the second resist underlayer film;
(e) generating a pattern of radiation-exposed regions in the radiation-sensitive image layer by exposing the radiation-sensitive imaging layer to radiation in a patterned fashion;
(f) selectively removing portions of the radiation-sensitive imaging layer and the second resist underlayer film to expose portions of the first resist underlayer film;
(g) selectively removing portions of the patterned second resist underlayer film and the first resist underlayer film to expose portions of the material layer; And
(h) etching the exposed portions of the material layer to form a patterned material shape.
Further comprising forming an antireflection film between the step (c) of forming the second resist underlayer film and the step (d) of forming the radiation-sensitive imaging layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170041847A (en) * | 2014-08-14 | 2017-04-17 | 어플라이드 머티어리얼스, 인코포레이티드 | Method for critical dimension reduction using conformal carbon films |
| JP2018055068A (en) * | 2016-09-30 | 2018-04-05 | Jsr株式会社 | Film-forming material for multilayer resist process and pattern forming method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170041847A (en) * | 2014-08-14 | 2017-04-17 | 어플라이드 머티어리얼스, 인코포레이티드 | Method for critical dimension reduction using conformal carbon films |
| JP2018055068A (en) * | 2016-09-30 | 2018-04-05 | Jsr株式会社 | Film-forming material for multilayer resist process and pattern forming method |
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